High-throughput device for hydrogen-free titanium-doped ta-C coating of large-area bipolar plate and preparation method of hydrogen-free titanium-doped ta-C coating

Abstract

The invention discloses a large-area bipolar plate hydrogen-free titanium doped ta-C coating high-flux device and a preparation method, the large-area bipolar plate hydrogen-free titanium doped ta-C coating high-flux device comprises a reaction cavity, a four-target closed field unbalanced magnetron sputtering system is arranged on the reaction cavity, and an extraction opening and a working gas input opening are formed in the reaction cavity; the four-target closed field unbalanced magnetron sputtering system comprises a cylindrical vacuum chamber, two sets of cylindrical targets are arranged on the side wall of the cylindrical vacuum chamber, cathodes of the four cylindrical targets are arranged in a 90-degree mode to form the closed field unbalanced system, the input end of the first set of cylindrical targets is connected with the output end of a pulse direct-current magnetron sputtering power source, and the output end of the second set of cylindrical targets is connected with the output end of a pulse direct-current magnetron sputtering power source. And the input end of the second group of cylindrical target materials is connected with the output end of the high-power pulse magnetron sputtering power supply. The sputtering power supply mode of the four target materials adopts composite deposition of a high-power pulse magnetron sputtering power supply and a pulse direct-current magnetron sputtering power supply, so that high ionization rate and high deposition rate of the target materials are ensured, and component and structure optimization of the hydrogen-free titanium doped ta-C coating of the bipolar plate is promoted.

Description

Technical Field

[0001] The present invention relates to the technical field of carbon-based coating preparation, and in particular to a high-throughput device and a preparation method for a large-area bipolar plate hydrogen-free titanium-doped ta-C coating. Background Art

[0002] A fuel cell is a device that converts chemical energy into electrical energy, and has the advantages of high efficiency, low pollution and zero emissions. Among them, metal bipolar plates, as one of the main components of fuel cells, directly affect the performance and service life of fuel cells. When using hydrogen-containing gases, such as acetylene gas and methane, reactive sputtering to prepare carbon-based compounds will leave residual hydrogen, which will cause the coating to crack, fall off and fail during use, seriously affecting the life of the metal bipolar plates.

[0003] Magnetron sputtering is a vacuum coating technology that introduces a magnetic field on the target cathode surface and uses the magnetic field to constrain charged particles to increase the plasma density and increase the sputtering rate, achieving high-speed, low-temperature, and low-damage sputtering. It has the advantages of simple equipment, easy control, large coating area, and strong adhesion. At present, magnetron sputtering has been widely used in the preparation of surface coatings for fuel cell metal bipolar plates.

[0004] In order to improve the performance and service life of fuel cells, it is necessary to prepare a hydrogen-free carbon-based coating to improve the conductivity and corrosion resistance of metal bipolar plates, while reducing the hydrogen-based carbon content of the coating to improve the efficiency and stability of fuel cells. Therefore, a high-throughput device and preparation method for hydrogen-free titanium-doped ta-C coatings for large-area bipolar plates is needed. Summary of the invention

[0005] The object of the present invention is to provide a high-throughput device method and system for large-area bipolar plate hydrogen-free titanium-doped ta-C coating.

[0006] To achieve the above object, the present invention is implemented according to the following technical solutions:

[0007] The present invention includes a reaction chamber, characterized in that a four-target closed-field unbalanced magnetron sputtering system is arranged on the reaction chamber, a gas extraction port and a working gas input port are arranged on the reaction chamber, the four-target closed-field unbalanced magnetron sputtering system includes a cylindrical vacuum chamber, two groups of cylindrical targets are arranged on the side walls of the cylindrical vacuum chamber, and the cathodes of the four cylindrical targets are arranged at 90° to each other to form a closed-field unbalanced system, the input end of the first group of cylindrical targets is connected to the output end of a pulsed DC magnetron sputtering power supply, and the input end of the second group of cylindrical targets is connected to the output end of a high-power pulsed magnetron sputtering power supply.

[0008] Furthermore, a bias power supply is provided in the reaction chamber, and a power supply output end of the bias power supply is respectively connected to the high-power pulsed magnetron sputtering power supply and a power supply input end of the high-power pulsed magnetron sputtering power supply.

[0009] Furthermore, a vacuum pump group is provided on the reaction chamber to maintain the vacuum degree of the reaction chamber.

[0010] Furthermore, the two groups of cylindrical targets are any one of high-purity Ti, Cr and C targets.

[0011] Furthermore, the working gas at the working gas input port is argon and nitrogen.

[0012] Furthermore, the four-target closed-field unbalanced magnetron sputtering system controls the vacuum control system and the gas path control system through a computer to adjust the working gas pressure, gas flow rate and pulse power supply parameters.

[0013] On the other hand, a high-throughput preparation method of a large-area bipolar plate hydrogen-free titanium-doped ta-C coating comprises the following steps:

[0014] A. Pretreatment and sample loading: After cleaning the stainless steel bipolar plate in an ultrasonic water bath, take out compressed air to dry the surface of the stainless steel bipolar plate. The cleaning time is 30 minutes. The stainless steel bipolar plate is vacuumed to 1×10 -4 Below Pa;

[0015] B. Ion cleaning: Place the metal bipolar plate into the reaction chamber, introduce argon gas at 80-120 sccm, set the pressure at 0.8-1.4 Pa, set the negative bias voltage at -500-800 V, and the ion cleaning time at 30-60 min.

[0016] C surface activation: sputtering power 6-8kW, micro pulse width on time 2-10μs / off time 60μs, negative bias setting -500-800V, sample stage speed 2rpm, time 6-10min;

[0017] D Preparation of hydrogen-free carbon-based coating: Set the sputtering power to 8-10kW, the argon flow rate to 80-120sccm, the gas pressure to 0.8-1.5Pa, the micro-pulse width on time to 2-8μs, the off time to 30μs, and the negative bias voltage to -300~

[0018] -500V, sample stage speed 1~2rpm, time about 10min, coating thickness is about 3~5μm. It can prepare smooth and dense bonding large-area bipolar plate hydrogen-free titanium-doped ta-C coating at high speed on the surface of metal, glass, ceramic and polymer.

[0019] Furthermore, the hydrogen-free titanium doped ta-C coating of the bipolar plate comprises a bonding layer and a hydrogen-free titanium doped ta-C coating, and the bonding layer is Cr or Ti metal.

[0020] Furthermore, the effective deposition coating area of ​​the bipolar plate coating is 1.2m×1.2m, the deposition rate is 25-100nm / s, and the contact resistance ICR is ≤3mΩ·cm 2 .

[0021] The beneficial effects of the present invention are:

[0022] The present invention is a high-throughput device method and system for large-area bipolar plate hydrogen-free titanium doped ta-C coating. Compared with the prior art, the present invention has the following technical effects:

[0023] 1. The present invention uses four cylindrical targets, and four target cathodes form a closed field non-equilibrium system, which can apply high sputtering power and high deposition rate;

[0024] 2. The sputtering power supply mode of the four targets of the present invention adopts a high-power pulse magnetron sputtering power supply and a pulse DC magnetron sputtering power supply for composite deposition, thereby ensuring a high ionization rate and a high deposition rate of the target materials.

[0025] 3. The ion energy control of the present invention increases the target material ionization rate and the deposition ion energy through high sputtering power and high negative bias voltage, and promotes the composition and structure optimization of the hydrogen-free titanium-doped ta-C coating of the bipolar plate.

[0026] 4. The present invention obtains high-quality coatings by regulating plasma reaction through high-power pulse width, peak power, negative bias voltage, and working gas. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 It is a schematic structural diagram of a high-throughput device for a large-area bipolar plate hydrogen-free titanium-doped ta-C coating according to the present invention;

[0028] Figure 2 A schematic diagram of the corrosion current density of the metal bipolar plate prepared by a high-throughput preparation method of a large-area bipolar plate hydrogen-free titanium-doped ta-C coating according to the present invention;

[0029] Figure 3 A schematic diagram of a sample photo of the metal bipolar plate after corrosion of the large-area bipolar plate without hydrogen-titanium doped ta-C coating of the present invention; DETAILED DESCRIPTION

[0030] The present invention is further described below with specific examples. The illustrative examples and descriptions of the present invention are used to explain the present invention but are not intended to limit the present invention.

[0031] The high-throughput device method of the large-area bipolar plate hydrogen-free titanium doped ta-C coating of the present invention comprises the following steps:

[0032] like Figure 1 As shown, the present invention includes a reaction chamber, characterized in that a four-target closed-field unbalanced magnetron sputtering system is arranged on the reaction chamber, a gas extraction port and a working gas input port are arranged on the reaction chamber, the four-target closed-field unbalanced magnetron sputtering system includes a cylindrical vacuum chamber, two groups of cylindrical targets are arranged on the side walls of the cylindrical vacuum chamber, and the cathodes of the four cylindrical targets are arranged at 90° to each other to form a closed-field unbalanced system, the input end of the first group of cylindrical targets is connected to the output end of a pulsed DC magnetron sputtering power supply, and the input end of the second group of cylindrical targets is connected to the output end of a high-power pulsed magnetron sputtering power supply.

[0033] In this embodiment, a bias power supply is provided in the reaction chamber, and a power supply output end of the bias power supply is respectively connected to the high-power pulsed magnetron sputtering power supply and the power supply input end of the high-power pulsed magnetron sputtering power supply.

[0034] In this embodiment, a vacuum pump group is provided on the reaction chamber to maintain the vacuum degree of the reaction chamber.

[0035] In this embodiment, the two groups of cylindrical targets are any one of high-purity Ti, Cr and C targets.

[0036] In this embodiment, the working gas at the working gas input port is argon and nitrogen.

[0037] In this embodiment, the four-target closed-field unbalanced magnetron sputtering system controls the vacuum control system and the gas path control system through a computer to adjust the working gas pressure, gas flow rate and pulse power supply parameters.

[0038] On the other hand, a high-throughput preparation method of a large-area bipolar plate hydrogen-free titanium-doped ta-C coating comprises the following steps:

[0039] A. Pretreatment and sample loading: After cleaning the stainless steel bipolar plate in an ultrasonic water bath, take out compressed air to dry the surface of the stainless steel bipolar plate. The cleaning time is 30 minutes. The stainless steel bipolar plate is vacuumed to 1×10 -4 Below Pa;

[0040] B. Ion cleaning: Place the metal bipolar plate into the reaction chamber, introduce argon gas at 80-120 sccm, set the pressure at 0.8-1.4 Pa, set the negative bias voltage at -500 to -800 V, and the ion cleaning time at 30-60 min.

[0041] C surface activation: sputtering power 6-8kW, micro pulse width on time 2-10μs / off time 60μs, negative bias setting -500-800V, sample stage speed 2rpm, time 6-10min;

[0042] D Preparation of hydrogen-free carbon-based coating: Set the sputtering power to 8-10kW, the argon flow rate to 80-120sccm, the gas pressure to 0.8-1.5Pa, the micro-pulse width on time to 2-8μs, the off time to 30μs, and the negative bias voltage to -300~

[0043] -500V, sample stage speed 1~2rpm, time about 10min, coating thickness is about 3~5μm. It can prepare smooth and dense bonding large-area bipolar plate hydrogen-free titanium-doped ta-C coating at high speed on the surface of metal, glass, ceramic and polymer.

[0044] In this embodiment, the hydrogen-free titanium doped ta-C coating of the bipolar plate includes a bonding layer and a hydrogen-free titanium doped ta-C coating, and the bonding layer is Cr or Ti metal.

[0045] In this embodiment, the effective deposition coating area of ​​the bipolar plate coating is 1.2m×1.2m, the deposition rate is 25-100nm / s, and the contact resistance ICR is ≤3mΩ·cm 2 .

[0046] like Figure 2 As shown, after testing, the contact resistance of the bipolar plate coating can reach 1.2mΩ·cm 2 ,80℃ corrosion current density: 0.191μA·cm -2 The photo of the sample after corrosion is as follows Figure 3 shown.

[0047] The present invention can achieve an effective deposition coating area of ​​1.2m×1.2m, a deposition rate of 25-100nm / s, and a contact resistance ICR of ≤3mΩ·cm 2 , corrosion current density ≤ 0.2μA·cm -2 The large-area bipolar plate hydrogen-free titanium doped ta-C coating and its high-throughput preparation technology involved in the present invention can accurately control the performance of the coating by adjusting the parameters of the micro-pulse, with fast deposition rate, simple operation and low cost. In addition, the method does not use flammable and explosive acetylene gas, which is safer and more reliable.

[0048] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. High-throughput device for large-area bipolar plates with hydrogen-free titanium-doped ta-C coating, including reaction chamber, Features The reaction chamber is provided with a four-target closed-field unbalanced magnetron sputtering system, and the reaction chamber is provided with an exhaust port and a working gas input port. The four-target closed-field unbalanced magnetron sputtering system includes a cylindrical vacuum chamber, and the side walls of the cylindrical vacuum chamber are provided with two groups of cylindrical targets. The cathodes of the four cylindrical targets are arranged at 90° to each other to form a closed-field unbalanced system. The input end of the first group of cylindrical targets is connected to the output end of a pulsed DC magnetron sputtering power supply, and the input end of the second group of cylindrical targets is connected to the output end of a high-power pulsed magnetron sputtering power supply.

2. The high-throughput device of the large-area bipolar plate hydrogen-free titanium-doped ta-C coating according to claim 1, It is characterized in that A bias power supply is arranged in the reaction chamber, and a power supply output end of the bias power supply is respectively connected to the high-power pulse magnetron sputtering power supply and the power supply input end of the high-power pulse magnetron sputtering power supply.

3. According to claim 1, a high-throughput device for large-area bipolar plate hydrogen-free titanium-doped ta-C coating, It is characterized in that The reaction chamber is provided with a vacuum pump group for maintaining the vacuum degree of the reaction chamber.

4. According to claim 1, a high-throughput device for large-area bipolar plate hydrogen-free titanium-doped ta-C coating, It is characterized in that The two groups of cylindrical targets are any one of high-purity Ti, Cr and C targets.

5. According to claim 1, a high-throughput device for large-area bipolar plate hydrogen-free titanium-doped ta-C coating, It is characterized in that The working gas at the working gas input port is argon and nitrogen.

6. The high-throughput device of the large-area bipolar plate hydrogen-free titanium-doped ta-C coating according to claim 1, It is characterized in that The four-target closed-field unbalanced magnetron sputtering system controls the vacuum control system and the gas path control system through a computer to adjust the working gas pressure, gas flow rate and pulse power supply parameters.

7. A high-throughput preparation method for a large-area bipolar plate hydrogen-free titanium doped ta-C coating, a high-throughput device for executing the large-area bipolar plate hydrogen-free titanium doped ta-C coating according to claims 1-6, It is characterized in that The following steps are involved: A. Pretreatment and sample loading: After cleaning the stainless steel bipolar plate in an ultrasonic water bath, take out compressed air to dry the surface of the stainless steel bipolar plate. The cleaning time is 30 minutes. The stainless steel bipolar plate is vacuumed to 1×10 -4 Below Pa; B. Ion cleaning: Place the metal bipolar plate into the reaction chamber, introduce argon gas at 80-120 sccm, set the pressure at 0.8-1.4 Pa, set the negative bias voltage at -500 to -800 V, and the ion cleaning time at 30-60 min. C surface activation: sputtering power 6~8kW, micro pulse width on time 2-10μs / off time 60μs, The negative bias voltage was set to -500 to -800 V, the sample stage speed was 2 rpm, and the time was 6 to 10 min; D Preparation of hydrogen-free carbon-based coating: set the sputtering power to 8-10kW, argon flow rate to 80-120sccm, gas pressure to 0.8-1.5Pa, micro-pulse width on time to 2-8μs, off time to 30μs, negative bias voltage to -300-500V, sample stage speed to 1-2rpm, time to about 10min, coating thickness to about 3-5μm. High-speed preparation of smooth, dense, and large-area bipolar plate hydrogen-free titanium-doped ta-C coatings on metal, glass, ceramic, and polymer surfaces.

8. A high-throughput preparation method for a large-area bipolar plate hydrogen-free titanium-doped ta-C coating according to claim 1, It is characterized in that The hydrogen-free titanium doped ta-C coating of the bipolar plate comprises a bonding layer and a hydrogen-free titanium doped ta-C coating, wherein the bonding layer is Cr or Ti metal.

9. A high-throughput preparation method for a large-area bipolar plate hydrogen-free titanium-doped ta-C coating according to claim 1, It is characterized in that The effective deposition coating area of ​​the bipolar plate coating is 1.2m×1.2m, the deposition rate is 25~100nm / s, and the contact resistance ICR is less than 3mΩ·cm 2 .

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